EP0926099B1 - Particules de magnetite et procédé de leur production - Google Patents

Particules de magnetite et procédé de leur production Download PDF

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Publication number
EP0926099B1
EP0926099B1 EP98124355A EP98124355A EP0926099B1 EP 0926099 B1 EP0926099 B1 EP 0926099B1 EP 98124355 A EP98124355 A EP 98124355A EP 98124355 A EP98124355 A EP 98124355A EP 0926099 B1 EP0926099 B1 EP 0926099B1
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Prior art keywords
component
particle
silicon
magnetite
aluminum
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EP98124355A
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German (de)
English (en)
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EP0926099A1 (fr
Inventor
Masachika Hashiuchi
Takeshi Miyazono
Masahiro Miwa
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/083—Magnetic toner particles
    • G03G9/0831—Chemical composition of the magnetic components
    • G03G9/0834—Non-magnetic inorganic compounds chemically incorporated in magnetic components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/083—Magnetic toner particles
    • G03G9/0835—Magnetic parameters of the magnetic components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/083—Magnetic toner particles
    • G03G9/0836—Other physical parameters of the magnetic components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/083—Magnetic toner particles
    • G03G9/0837—Structural characteristics of the magnetic components, e.g. shape, crystallographic structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • the present invention relates to magnetite particles. More particularly, the invention relates to magnetite particles which have a silicon component, an aluminum component, and a metal element other than iron, both at the center of and on the surface of the particles, and in which the amounts of the silicon component, the aluminum component and the metal element dispersed near the surface of the particle, and the amounts of the silicon component and the aluminum component exposed on the surface of the particle are controlled, whereby the properties of the magnetite particles, such as oil absorption, electrical resistance, magnetic characteristics, and environmental resistance, are improved in a well-balanced manner.
  • the magnetite particles are mainly used as a starting powder for magnetic toners for electrostatic copying, and as black pigment powders for paints.
  • the invention also concerns a process for producing such magnetite particles.
  • magnetite particles produced by a reaction in an aqueous solution have been widely used as a material for a magnetic toner for electrophotographic copiers or printers.
  • Various general development characteristics are required of the magnetic toner.
  • outputs such as graphics or photographs have been required in addition to conventional character outputs.
  • printers in particular, those capable of printing 1,200 dots or more per inch have appeared, making latent images on the photoconductor even more meticulous.
  • Japanese Unexamined Patent Publication No. 72801/93 discloses a magnetic toner wherein a magnetic powder with high resistance and good flowability is desired.
  • magnetic iron oxide is described as still requiring an improvement in environmental resistance.
  • a magnetic powder is desired which not only possesses the required properties for production of a toner, but is also excellent in environmental resistance (moisture resistance).
  • Japanese Unexamined Patent Publication No. 239571/95 points out that the environmental resistance of a magnetic powder, especially under hot humid conditions, is problematical.
  • a magnetic toner in Japanese Unexamined Patent Publication No. 1160/91, high resistance and low hygroscopicity are needed to show the required performance in diverse environments. To eliminate scatter over images, a magnetic toner should be low in coercive force and residual magnetization.
  • toner is classified into negatively chargeable toner and positively chargeable toner.
  • Resin carriers comprising magnetite or the like also come in a negative charge type and a positive charge type.
  • Japanese Unexamined Patent Publication No. 110598/95 corresponding to EP 0 652 490 A discloses magnetite particles containing a silicon component inside the particle, and having the silicon component and an aluminum component precipitated and deposited on the surface of the particle as a coprecipitate.
  • improvement achieved in the image density and the flowability are still insufficient.
  • the surface of the particle is covered with the silicon and aluminum components.
  • the environmental resistance due to moisture absorption is unsatisfactory, and many agglomerates appear.
  • Japanese Unexamined Patent Publication No. 170325/92 discloses a process for producing particles having high coercive force and high residual magnetization by coating the surface of particles, which contain or do not contain a silicon component and an aluminum component, with silicon or aluminum, followed by oxidation or reduction.
  • this publication does not have as an object the provision of magnetite particles having low residual magnetization and low coercive force, having high electrical resistance, excellent in workability, flowability, dispersibility and environmental resistance, and arbitrarily adjustable in charging properties according to a purpose to be attained, and a process for producing such magnetite particles.
  • the intermediate product before oxidation or reduction also has the same drawbacks.
  • Japanese Unexamined Patent Publication No. 213620/93 discloses magnetite particles containing a silicon component at the center and on the surface thereof, and having well balanced residual magnetization, satisfactory flowability, and high electrical resistance. These particles give an image quality with improved thin line reproducibility, but are problematical in environmental stability because of hygroscopicity.
  • Japanese Unexamined Patent Publication No. 267646/95 discloses the production of a magnetic powder excellent in resistance to moisture absorption and magnetic characteristics by the use of silicic acid anhydride.
  • the silicon component used is silicic acid anhydride, which is added in the course of the reaction for forming particles.
  • silicic acid anhydride is present as independent fine particles in the resulting magnetite particles.
  • no silicon component is present at the center of the magnetite particle.
  • residual magnetization is high, and flowability is still insufficient.
  • Japanese Unexamined Patent Publication No. 59025/97 discloses a magnetic powder having high flowability and blackness obtained by the use of silicon, etc. However, the coercive force is high compared with the particle size, so that the improvement in thin line reproducibility of images and the flowability are still far from satisfactory.
  • the present invention has solved the above-described problems with the earlier technologies. Its object is to provide magnetite particles which are arbitrarily adjustable in charging properties according to the purpose; and a process for producing the magnetite particles.
  • the inventors achieved this object by incorporating a silicon component, an aluminum component, and a metal component other than iron, into the center of magnetite particles; coating an outer shell of the particles with a metal compound comprising at least one metal component bound to the silicon component and the aluminum component, the metal component being selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo and having a total amount of 0.01 to 0.5 wt.% of the silicon component and the aluminum component exposed on the surface of the particles.
  • the outer shell of the particle in the present description refers to a portion in which the iron (Fe), if dissolved from the surface of the particle, has been dissolved to a depth corresponding to a volume of 40 wt.% based on the total Fe content of the particle. A region from the site of this depth to the center of the particle is deemed to be an inner shell.
  • magnetite particles in which a gradient is provided such that the concentration, based on Fe, of any of the Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo components is higher in the outer shell than in an inner shell of the magnetite particle, and the total amount of any of the Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W and Mo components in the entire particle is 0.2 to 4.0 wt.%, based on the magnetite particle, expressed as any of the respective metal elements.
  • the magnetite particles have an oil absorption of not more than 20 ml/100 g, an electrical resistance of not lower than 1x10 4 ⁇ cm, and a moisture content, after moisture absorption under high-temperature, high-humidity conditions, of not more than 0.6%.
  • the magnetite particles have a residual magnetization ⁇ r of not more than 6 Am 2 /kg (emu/g), and a degree of agglomeration of not higher than 35%.
  • the magnetite particles of the present invention have the following features:
  • the magnetite particles of the present invention require that the silicon component and the aluminum component in the particle be contained continuously in the region from the center to the surface of the particle, and that the silicon component and the aluminum component be contained in the surface of the particle. If part of the silicon component and the aluminum component is not exposed on the surface even when silicon and aluminum exist in the center of the magnetite particle, the particles will have poor flowability, and contribute minimally to an improvement in electrical resistance.
  • the silicon component and the aluminum component are present only on the surface of the particle, on the other hand, the residual magnetization and the coercive force will become high relative to the particle size, making the properties un-balanced. If the presence of the silicon component and the aluminum component is not continuous from the center to the surface of the particle, an effect resulting from the binding of the silicon component and the aluminum component to the metal component (to be described later on) will be poor.
  • the total amount of the silicon component and the aluminum component, expressed as silicon and aluminum, based on the entire magnetite particle (may be referred to as the total amount of Si and Al) is 0.2 to 1.2 wt.%. If the total amount of Si and Al is less than 0.2 wt.%, the magnetite particles will be inferior with minimal effect on the residual magnetization, coercive force, and flowability. If the total amount of Si and Al exceeds 1.2 wt.%, the electrical resistance, residual magnetization, coercive force, and flowability will be fully improved, but the environmental resistance will be deteriorated as typified by high hygroscopicity. Besides, this is not economical.
  • the compound of the silicon component and the aluminum component with the metal component refers to a compound oxide having a silicon component and an aluminum component incorporated into a metal oxide or hydroxide.
  • the silicon component and the aluminum component exposed on the surface of the particle are in amounts determined by the following analytical method:
  • the total amount of Si and Al in the entire magnetite particle is determined by ICP analysis using a sample dissolved in a hydrochloric acid-hydrofluoric acid solution.
  • the magnetite particles of the present invention need to have the silicon component and the aluminum component present both at the center of and on the surface of the magnetite particle as described earlier.
  • a compound of at least one metal component which is selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo, with the silicon component and the aluminum component be present in an outer shell of the particle.
  • the total amount of any of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo present in the particle is preferably 0.2 to 4.0 wt.% expressed as any of the respective metal elements (hereinbelow, "the amount of the metal component" refers to the amount expressed as metal element).
  • the metal component is less than 0.2 wt.%, there will be insufficiency in the formation of the metal compound comprising at least one metal component bound to the silicon component and the aluminum component in the outer shell of the particle, the metal component being selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W and Mo.
  • the effect of improving environmental resistance, electrical resistance, etc., the object of the present invention will be diminished.
  • the saturation magnetization will decline, and the oil absorption will increase. These are not preferred economically.
  • the at least one metal component in the particle that is selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo
  • it is more preferable to provide a gradient such that the concentration, based on Fe, of any of the Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo components is higher in the outer shell than in the inner shell of the magnetite particle.
  • the total amount of any of the Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo; components in the entire particle is preferably 0.2 to 4.0 wt.%, based on the magnetite particle, expressed as any of the respective metal elements.
  • the method of providing a gradient such that the above concentration is higher in the outer shell may be, but is not restricted to, a publicly known method, such as a continuous change in the concentration, adjustment of pH, or progressive addition of any of the metal components.
  • a publicly known method such as a continuous change in the concentration, adjustment of pH, or progressive addition of any of the metal components.
  • the effect of the invention cannot be fully obtained by the inorganic coating of the surface after completion of particle formation, thereby fixing an oxide or the like to the particle surface.
  • the magnetite particles of the invention preferably have an oil absorption of not more than 20 ml/100 g. If the oil absorption exceeds 20 ml/100 g, the miscibility and dispersibility of the particles with resin are likely to become lower. After formation into a toner, the magnetic powder may become exposed to the outside, or the toner may spill, affecting the image characteristics.
  • the magnetite particles of the invention preferably have an electrical resistance of 1x10 4 ⁇ cm or more.
  • a lower electrical resistance than 1x10 4 ⁇ cm would make it difficult for the toner to retain the required amount of electric charge, and is likely to exert adverse influences on toner characteristics, such as a decrease in image density.
  • the magnetite particles of the invention preferably have a moisture content, after moisture absorption under high-temperature, high-humidity conditions, of not more than 0.6%. At a moisture content in excess of 0.6%, there may be a decline in environmental resistance, especially, a deterioration in charge characteristics after being left for a long term under high humidity conditions.
  • the moisture content after moisture absorption under the high-temperature, high-humidity conditions is a value measured at 150°C by the Karl Fischer technique after moisture is absorbed for 3 days at 35° C and humidity of 85%.
  • the object of the present invention can be attained with the use of smaller amounts of silicon, aluminum and metal components than before, by making the silicon component and the aluminum component present continuously in a region from the center to the surface of the particle, making the silicon component and the aluminum component exposed on the surface, and incorporating the metal component, and more preferably, by concentrating the silicon component, the aluminum component and the metal component in a more outward portion of the magnetite particle.
  • the reason why the magnetite particles of the invention have achieved the intended object of the invention is not clear. However, it is presumed as follows: The compound comprising the silicon component, the aluminum component, and at least one metal component bound thereto which is selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo; has coated the outer shell of the particles uniformly. That is, because of the formation of this metal compound, the silicon component and the aluminum component of the invention turn into very fine particles. Thus, as magnetite particles grow, such fine particles are taken up into the matrix particles smoothly and uniformly. Eventually, a thin, uniform layer of the silicon component and the aluminum component is exposed on the surface of the magnetite particles. Even this small amount of the surface-exposed silicon component and aluminum component gives sufficient flowability. Moreover, its synergistic effect has resulted in the acquisition of magnetite particles having smooth particle surfaces, and possessing high electrical resistance and excellent environmental resistance.
  • the magnetite particles of the invention have magnetic characteristics well balanced against the particle size, are low in residual magnetization and coercive force, and high in the concentrations of the silicon component, the aluminum component and the metal component, other than Fe, present on the surface of the particle. This may reduce magnetic agglomeration, further contributing to flowability and dispersibility.
  • aqueous solution consisting essentially of a ferrous salt, a silicon component, an aluminum component, and 1.0 to 1.1 equivalents, based on iron, of an alkali are mixed.
  • the preferred ferrous salt is ferrous sulfate.
  • the preferred silicon component is a solution containing a hydrous silicate colloid prepared from a silicic acid compound.
  • a silicic acid compound including a hydrous compound
  • the aluminum component is used similarly.
  • an aluminic acid compound (including a hydrous compound) can be formed in the resulting particles by using sodium aluminate or aluminum sulfate.
  • An oxygen-containing gas preferably, air
  • the amount of this oxidation reaction is controlled by analyzing the amount of the unreacted ferrous hydroxide, and adjusting the amount of the oxygen-containing gas, during the reaction. In this oxidation reaction, it is vital to maintain the pH at 7 to 10, preferably 7 to 9.
  • a supplementary amount of iron to achieve 0.9 to 1.2 equivalents, preferably 1.05 to 1.15 equivalents, based on the initial alkali, is added during the oxidation reaction.
  • the iron used here is desirably in the form of a solution containing a ferrous salt such as ferrous sulfate.
  • the oxidation reaction is continued with the pH being maintained at 6 to 10, preferably 6 to 9, to grow particles.
  • an aqueous solution containing at least one metal component selected from the group consisting of Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg , Ti, Ce, W and Mo; is added to the reaction system.
  • the metal element added for this purpose may be in the form of an aqueous solution or a hydroxide. If two or more metal components are added, they may be added separately or as a mixture.
  • reaction system is washed, filtered, dried and ground by the customary methods to obtain magnetite particles.
  • pH during the oxidation reaction is preferably adjusted to 6 to 10, more preferably 6 to 9, as described earlier. This is because if the pH during the oxidation reaction is higher than 9, the silicon component and the aluminum component will be easily taken up into the center of the magnetite particle. Consequently, the amounts of the silicon component and the aluminum component present in the outer shell and exposed on the surface of the particle will be inadequate. The formation of a compound of the silicon component and the aluminum component bound to the metal component will also be insufficient. In the contrary case, the silicon component and the aluminum component will be minimally incorporated into the center of the particle, and will be precipitated on the surface.
  • the progress rate of the reaction was examined halfway with the concentration of the unreacted ferrous hydroxide being checked.
  • 10 L of an aqueous solution of nickel sulfate in a concentration of 0.1 mol/L was added over the course of about 100 minutes to a ferrous hydroxide slurry containing magnetite continued in the oxidation reaction.
  • the pH maintained at 6 to 9
  • the oxidation reaction was continued and then completed.
  • the resulting magnetite slurry after completion of the reaction was washed, filtered, dried and ground by the customary methods.
  • the so obtained magnetite particles had an amount of Si of 0.6 wt.%, an amount of Al of 0.6 wt.%, a total amount of Si and Al of 1.2 wt.%, an amount of surface-exposed Si of 0.13 wt.%, an amount of surface-exposed Al of 0.17 wt.%, a total amount of surface-exposed Si and Al of 0.30 wt.%, and a total amount of Ni of 0.5 wt.%.
  • These magnetite particles were measured for the A 20 atomic %, A 40 atomic %, particle size, magnetic characteristics, electrical resistance, degree of agglomeration, moisture content after moisture absorption under high-temperature, high-humidity conditions, oil absorption, and amount of charge. The results are shown in Table 1.
  • the diameters of the particles were measured from a transmission electron micrograph (X30,000), and the average of the particle diameters was taken as the particle size.
  • VSM-P7 vibration sample type magnetometer
  • Magnetite particles were predried in a dryer at 150°C, and allowed to absorb moisture for 3 days at 35°C and 85% RH by the use of a high temperature, high humidity tester ("LHL-111", TABAI ESPEC CORP.). Then, moisture in the magnetite particles was evaporated at 150°C by "WATER VAPORIZER VA-05” (Mitsubishi Chemical Corp.), and detected by "MOISTURE METER CA-03" (MITSUBISHI KASEI Corporation) to determine the moisture content of the magnetite particles.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.3 wt.%, 0.2 wt.%, 0.14 wt.%, and 4.0 wt.%, respectively, that the types of metals added during the reaction were Zn, Co, Ni, Mg, Ti and Mn, and that the pH for the reaction after addition of the supplementary amount of iron was varied in the range of 6 to 10.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.8 wt.%, 0.1 wt.%, 0.41 wt.%, and 3.0 wt.%, respectively, that the types of metals added during the reaction were Zn, Mn and Cu, and that the pH for the reaction after addition of the supplementary amount of iron was varied in the range of from 6 to 8.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.1 wt.%, 0.4 wt.%, 0.10 wt.%, and 1.4 wt.%, respectively, and that the types of metals added during the reaction were Zn, Mn and Zr.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.2 wt.%, 0.1 wt.%, 0.04 wt.%, and 2.6 wt.%, respectively, and that the types of metals added during the reaction were Zn, Mn, Cu and Ni.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.1 wt.%, 0.8 wt.%, 0.02 wt.%, and 0.3 wt.%, respectively, that the type of metal added during the reaction was Co, and that the pH for the reaction after addition of the supplementary amount of iron was varied in the range of from 6 to 9.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.01wt.%, 0.99wt.%, 0.30wt.%, and 1.9wt.%, respectively, that the types of metals added during the reaction were Cr, Zr, Sn and Cu, and that the pH for the reaction after addition of the supplementary amount of iron was varied in the range of from 6 to 9.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of surface exposed Si and Al, and the total amount of metals were adjusted to 0.5 wt.%, 0.1 wt.%, 0.15 wt.%, and 1.5 wt.%, respectively, that the types of metals added during the reaction were Ce, W, and Mo, and that the pH for the reaction after addition of the supplementary amount of iron was varied in the range of from 6 to 9.
  • Magnetite particles were obtained by the same procedure as in Example 4, except that the gradient of the metal component in the particle was varied.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that no metal was added, and that the amount of Si, the amount of Al, and the total amount of surface exposed Si and Al were set at 1.2 wt.%, 0.6 wt.%, and 0.73 wt.%, respectively.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that the amount of Si, the amount of Al, the total amount of metals, and the total amount of surface exposed Si and Al were set at 0.4 wt.%, 0.2 wt.%, 2.9 wt.%, and 0 wt.%, respectively, the types of metals added during the reaction were Zn, Mn and Ni, and the pH for the reaction after addition of the supplementary amount of iron was varied in the range of from 10 to 11.
  • Magnetite particles were obtained by the same procedure as in Example 2, except that the total amount of the metals was adjusted to 5.5 wt.%.
  • Magnetite particles were obtained by the same procedure as in Example 1, except that no Si or Al was added, the total amount of metals was adjusted to 1.9 wt.%, and the types of metals added during the reaction were Zn, Mn and Zr.
  • the magnetite particles of Examples 1 to 8 obtained by the present invention were satisfactory in all of electrical resistance, residual magnetization, oil absorption, moisture content, and degree of agglomeration.
  • the amount of charge was also adjustable in a range from negative values to positive values.
  • the magnetite particles of Comparative Example 1 had a large total amount of Si and Al, and large amounts of Si and Al were exposed on the surface of the particles. Thus, the electrical resistance and the degree of agglomeration were satisfactory, but the oil absorption and the moisture content were both high.
  • the silicon component and the aluminum component are present continuously in the region from the center to the surface of the particle, and the surface of the particle is coated with the metal component bound to the silicon component and the aluminum component, the metal component being specified ih the various aspects of the invention.
  • the oil absorption is low
  • the electrical resistance is high
  • the magnetic characteristics, environmental resistance, and flowability are excellent
  • the amount of charge can be adjusted according to the intended purpose.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Claims (5)

  1. Particules de magnétite contenant de manière continue une quantité totale de 0,2 à 1,2 % en poids, sur la base de la magnétite, d'un composant de silicium et d'un composant d'aluminium, exprimée en silicium et en aluminium, dans une zone allant du centre à la surface de la particule ;
       une quantité totale de 0,01 à 0,5 % en poids du composant de silicium et du composant d'aluminium, exprimée en silicium et en aluminium, étant exposée sur la surface de la particule ; et
       une couche externe de la particule étant revêtue avec un composé métallique comprenant au moins un composant métallique lié au composant de silicium et au composant d'aluminium, ledit composant métallique étant choisi dans le groupe constitué de Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W et Mo.
  2. Particules de magnétite selon la revendication 1, dans lesquelles on crée un gradient tel que la concentration, sur la base de Fe, de l'un quelconque des composants de Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W et Mo soit plus élevée dans la couche externe que dans une couche interne de la particule de magnétite, et que la quantité totale de l'un quelconque des composants de Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W et Mo dans la particule entière soit de 0,2 à 4,0 % en poids, sur la base de la particule de magnétite, exprimée sous la forme de l'un quelconque des éléments métalliques respectifs.
  3. Particules de magnétite selon la revendication 1 ou 2, qui ont une absorption d'huile non supérieure à 20 ml/100 g, une résistance électrique non inférieure à 1 x 104 Ωcm, et une teneur en humidité, après absorption d'humidité dans des conditions de haute-température, haute-humidité, non supérieure à 0,6 %.
  4. Particules de magnétite selon la revendication 1 ou 2, qui ont une magnétisation résiduelle σr non supérieure à 6 Am2/kg (emu/g), et un degré d'agglomération non supérieur à 35 %
  5. Procédé de production de particules de magnétite selon la revendication 1, comprenant le fait de :
    mélanger d'une solution aqueuse constituée essentiellement d'un sel ferreux, d'un composant de silicium, d'un composant d'aluminium, et de 1,0 à 1,1 équivalents, sur la base du fer, d'un alcali,
    effectuer une réaction d'oxydation du mélange tout en maintenant son pH de 7 à 10 ;
    ajouter une quantité supplémentaire de fer pour obtenir 0,9 à 1,2 équivalents sur la base de l'alcali initial, pendant la réaction ;
    continuer la réaction d'oxydation tout en maintenant le mélange à un pH de 6 à 10 ; et
    ajouter au moins un composant métallique choisi dans le groupe constitué de Zn, Mn, Cu, Ni, Co, Cr, Cd, Zr, Sn, Mg, Ti, Ce, W et Mo, après l'addition de la quantité supplémentaire de fer, tout en ajustant la concentration du ou des composants métalliques pour qu'elle soit supérieure dans une couche externe de la particule et supérieure dans une partie superficielle de la particule.
EP98124355A 1997-12-26 1998-12-21 Particules de magnetite et procédé de leur production Expired - Lifetime EP0926099B1 (fr)

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JP35916497 1997-12-26
JP35916497A JP3261088B2 (ja) 1997-12-26 1997-12-26 マグネタイト粒子およびその製造方法

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WO2003033407A1 (fr) 2001-10-15 2003-04-24 Mitsui Mining & Smelting Company, Ltd. Particules d'oxyde de fer et procede d'elaboration
JP4018495B2 (ja) * 2002-09-27 2007-12-05 キヤノン株式会社 乾式トナー
JP2005024775A (ja) 2003-06-30 2005-01-27 Ricoh Co Ltd 静電荷像現像用トナー、画像形成方法及び画像形成装置用プロセスカートリッジ
EP1645914B1 (fr) 2004-10-08 2012-06-06 Canon Kabushiki Kaisha Révélateur magnétique
EP1645913B1 (fr) 2004-10-08 2011-03-16 Canon Kabushiki Kaisha Révélateur magnétique
JP2006313255A (ja) 2005-05-09 2006-11-16 Ricoh Co Ltd 静電荷現像用トナーの製造方法、静電荷現像用トナーおよび該トナーを含む一成分現像剤及び二成分現像剤
JP5136749B2 (ja) * 2006-04-28 2013-02-06 戸田工業株式会社 黒色磁性酸化鉄粒子粉末
JP5491708B2 (ja) * 2008-07-25 2014-05-14 三井金属鉱業株式会社 マグネタイト粒子及びその製造方法
JP5164715B2 (ja) 2008-07-25 2013-03-21 キヤノン株式会社 トナー
JP5517505B2 (ja) * 2009-06-30 2014-06-11 キヤノン株式会社 磁性トナー及びその製造方法
JP5546260B2 (ja) * 2010-01-22 2014-07-09 キヤノン株式会社 磁性トナー粒子の製造方法

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* Cited by examiner, † Cited by third party
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JPS5860753A (ja) * 1981-10-08 1983-04-11 Canon Inc 静電潜像現像用磁性トナー
US5356712A (en) * 1991-09-13 1994-10-18 Mitsui Mining & Smelting Co., Ltd. Magnetite particles
JPH0825747B2 (ja) * 1991-09-13 1996-03-13 三井金属鉱業株式会社 マグネタイト粒子およびその製造方法
US5648170A (en) * 1993-04-27 1997-07-15 Toda Kogyo Corporation Coated granular magnetite particles and process for producing the same
JP3259744B2 (ja) * 1993-10-08 2002-02-25 戸田工業株式会社 磁性トナー用磁性粒子粉末及びその製造法
US5599627A (en) * 1993-10-08 1997-02-04 Toda Kogyo Corporation Magnetic particles comprising magnetite core and process for producing the same
KR0163819B1 (ko) * 1994-08-05 1998-11-16 사코 유키오 마그네타이트 입자 및 그 제조방법
US5759435A (en) * 1996-05-23 1998-06-02 Mitsui Mining & Smelting Company, Ltd. Magnetite particles and process for production thereof
JP3224774B2 (ja) * 1997-09-25 2001-11-05 三井金属鉱業株式会社 マグネタイト粒子およびその製造方法

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EP0926099A1 (fr) 1999-06-30
DE69812566D1 (de) 2003-04-30
US6059988A (en) 2000-05-09
JPH11189420A (ja) 1999-07-13
DE69812566T2 (de) 2004-01-29
JP3261088B2 (ja) 2002-02-25

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